WO2002021921A1 - Oil suspension concentrates based on a cyclohexenone oxime ether lithium salt and the use thereof as plant protection agents - Google Patents

Abstract

The invention relates to oil suspension concentrates based on 2-{1-[2-(4-chlorophenoxy)-propoxyimino]-butyl}-3-hydroxy-5-(tetrahydrothiopyran-3-yl)-cyclohex-2-enone lithium salt and certain formulation auxiliary agents, in addition to the use of said oil suspension concentrates as plant protecting agents, especially rice herbicides. Preferred formulation auxiliary agents are monocarboxylic and/or dicarboxylic acid esters, e.g. liquid fatty acid esters; anionic surfactants such as sulfonates, e.g. alkyl and alkylaryl sulfonates and sulfosuccinates; and non-ionic surfactants such as optionally ethoxylated carboxylic acids and esters of monofunctional or polyfunctional alcohols, e.g. ethoxylated fatty acids and polyoxyethylene sorbitan fatty acid esters. The aforementioned oil suspension concentrates are stable in storage and have excellent properties of use.

Description

 I

Oil suspension concentrates based on a cyclohexenone oxime ether lithium salt and their use as crop protection agents.

The present invention relates to oil suspension concentrates based on 2- {l- [2- (4-chlorophenoxy) propoxyimino] butyl} -3-hydroxy-5- (tetrahydrothiopyran-3-y1) -cyclohex-2- enon lithium salt and certain formulation auxiliaries, and the use of the oil suspension concentrates as crop protection agents, in particular

10 as rice herbicides.

In addition to the optimization of the active ingredient properties, the development of an efficient crop protection agent is particularly important with regard to industrial production and application of these active ingredients

15 Meaning too. By properly formulating the active ingredient, it is necessary to find an optimal balance between contradicting properties such as biological effectiveness, toxicology, possible effects on the environment and costs.

20

In addition, the formulation significantly determines the shelf life of a plant protection product. This is particularly important if, due to instability of the active substance or unfavorable storage conditions, particularly high demands are placed on a plant protection product.

25

For example, suspension concentrates are of great practical importance. These are liquid, heterogeneous formulations of solid active substances in a liquid phase. Next

. ₀ the general advantages of liquid formulations with regard to handling and meterability, for example under ULV (Ultra Low Volume) conditions, suspension concentrates can moreover often be distinguished by good biological activity with relatively low phytotoxicity. Aqueous ones are typical

_ ₅ suspension concentrates. Occasionally, however, oily suspension concentrates are also described, the problem here being that many active substances and active substance salts are soluble in the oily phase that is usually used.

40 WO 00/35288 describes the formulation of glyphosates or glufosinates together with cyclohexenone oxime ethers as oil suspension concentrates. In addition to the free acids, salts of cyclohexenoneoxy ether are also considered there. However, due to insufficient stability, these proved to be unsuitable

45 has proven suitable as the formulation of the lithium salt of 2- {l- [2- (3-chloroallyloxy) iminopropyl] butyl} -3-hydroxy-5- (tetrahydropyran-3-yl) cyclohex-2- enone together with calcium glyphosate shows.

EP 0 313 317 describes oily suspension concentrates of certain sulfonylurea derivatives which can also be used in the form of their alkali, alkaline earth metal or ammonium salts. Vegetable oils, especially corn oil, and surface-active substances that can emulsify the vegetable oils in water are used. Similar oil-based suspension concentrates are described in US 5,411,932. Here, too, vegetable oils, in particular * ^■, "Separate corn oil and rapeseed oil, in addition, also mineral oils and surfactants are fonamids for the formulation of a specific sulfonic, nicosulfuron, or used a salt thereof. The insufficient in itself stability liquid sulfonylurea formulated Lation is countered by adding urea.

15

Cyclohexenone oxime ethers and their metal salts are generally known as valuable crop protection agents. They are particularly valued as grass herbicides. Cyclohexenone oxime ethers of the following formula (Ia) have proven to be particularly suitable herbicidal active ingredients

20 and metal salts thereof (WO 97/20807) proved:

However, it is already known from EP-A 266 068 that Herbi¬

35 cides from the class of cyclohexenone oxime ethers tend to decompose. The storage of appropriate crop protection formulations over a long period of time at higher temperatures is particularly critical. This also applies to the cyclohexenone oxime ethers of the formula (Ia) mentioned, including their metal salts.

40

In view of this problem, DE 195 10 887 describes storage-stable solid formulations which, in addition to a cyclohexenone oxime ether or a salt thereof, contain certain water-soluble basic salts, in particular certain borates, phosphates, silicates, sulfites, citrates, acetates and carbonates. These are water-soluble compositions, preferably in the form of powders or granules.

For the formulation of certain cyclohexenone oxime ether metal salts, WO 97/20807 mentions not only solid but also a large number of liquid formulations which are usually used in the field of crop protection. In this context, inert auxiliaries such as oils, lower alcohols, and strongly polar solvents, in particular water, and customary surface-active substances are mentioned, which are essentially to be considered for the formulations mentioned there. However, many of these auxiliaries as a corresponding formulation lead to rapid decomposition of the active ingredient.

The task of providing stable liquid formulations of the cyclohexenone oxime ether of the formula (Ia) with good biological performance is achieved by the present invention through oil suspension concentrates of the corresponding lithium salt based on certain carboxylic acid esters or selected surfactants from the series of the sulfonates and the modified ones carboxylic acids.

The present invention therefore relates in particular to oil suspension concentrates comprising

(al) 2- {l- [2- (4-chlorophenoxy) propoxyimino] butyl} -3-hydroxy-5- (tetrahydrothiopyran-3-yl) cyclohex-2-enone lithium salt of the formula (I)

and

at least one component selected under

(bl) at least one mono- and / or dicarboxylic acid ester of the formula (Ha) or (Ilb), R ^l -CO-OR ² (Ha)

R3-0-CO-A ¹ -CO-0-R4 (Ilb)

where R ¹ for a straight-chain or branched, saturated or unsaturated aliphatic radical

6 to 30 carbon atoms, R ^{2 represents} straight-chain or branched Ci-Cg-alkyl or C ₃ -Cι ₀ cycloalkyl, A ^{1 represents} straight-chain or branched C ₂ -C ₆ alkylene or C ₃ -Cιo-cycloalkylene and R ³ , R ⁴ independently of one another represent a straight-chain or branched, saturated or unsaturated aliphatic radical having 1 to 24 carbon atoms;

(cl) at least one anionic surfactant of the formula III,

R ⁵ -S0 ₃ - 1 / n M ^{(n +)} (III)

where M is a mono- or divalent cation (n = 1 or 2) and R ^{5 is} a straight-chain or branched, aliphatic or heteroaliphatic radical having 6 to 30 carbon atoms or a (C ₆ -C ₃ o-alkyl) aryl radical, and

(c2) at least one nonionic surfactant of the formula IV,

[R6-C0- (E0) _x -] _y A ² (IV)

where R ^{6 is} a straight-chain or branched, saturated or unsaturated, optionally mono- or dihydroxylated aliphatic radical having 8 to 30 carbon atoms, the sum of all x is from zero to 100, y is from 1 to 7, A ^{2 is} hydroxyl or Cι- C ₄ alkyloxy is when y is 1, or A ^{2 is derived} from a C ₃ -C ₇ polyol when y is 2 to

7 stands.

Accordingly, the present invention relates to liquid, heterogeneous active substance-containing formulations. They contain solid active ingredient that is distributed in an oily phase.

Oil suspension concentrates according to the invention are based on a

Active ingredient component (a) and a formulation component (F). If necessary, further additives can be included. The proportion of active ingredient component (a) in the oil suspension concentrate is variable. It is typically in a range from 1 to 70% by weight, preferably in a range from 5 to 50 and in particular in a range from 5 to 30% by weight. 5

In general, quantities are based on the total weight of the oil suspension concentrate, unless stated otherwise. According to the invention, the expression “essentially” generally denotes a percentage ratio of at least 90%, preferably of at least 95% and in particular of at least 98

Terms such as alkyl, alkoxy, etc. include straight-chain or branched hydrocarbon groups, such as methyl, ethyl, n-propyl, 5-i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, n- Hexyl, n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl, n-decyl, iso-decyl, n-undecyl, iso-undecyl, n-dodecyl, iso-dodecyl, n-tridecyl, iso-tridecyl, stearyl, n-eicosyl, preferably with - unless stated otherwise - 1 to 8, in particular 1 to 6 and 0 particularly preferably 1 to 4 carbon atoms for short-chain radicals and 6 to 30, in particular 8 to 24 and particularly preferably 12 to 24 carbon atoms for long chain residues.

The term "cycloalkyl" encompasses mono- or bicyclic, optionally one, two or three times substituted with C 1 -C ₄ -alkyl, saturated hydrocarbon groups, such as cyclopropyl, cyclobutyl, cyclopentyl and especially cyclohexyl, etc., preferably with - if nothing other is indicated - 3 to 10, in particular 3 to 6 and particularly preferably 6 carbon atoms. These explanations apply analogously to "cycloalkylene" as corresponding divalent radicals, of which the cycloalk-1,2-ylene are preferred.

The term "alkenyl" encompasses straight-chain or branched unsaturated hydrocarbon groups, which preferably have one, two 5 or three double bonds, such as ethenyl, prop-2-en-1-yl, oleyl, etc. , preferably with - unless stated otherwise - 3 to 8, in particular 2 to 6 and particularly preferably 2 to 4, carbon atoms for short-chain radicals and 6 to 30, in particular 8 to 24 and particularly preferably 12 to 24, carbon atoms for long-chain radicals.

The term "alkylene" encompasses straight-chain or branched divalent radicals, such as methylene, eth-1, 1-ylene, eth-1, 2-ylene, prop-1, 1-ylene, prop-1, 2-ylene, prop -l, 3-ylene, prop-2, 2-ylene, 5 but-1, 1-ylene, but-l, 2-ylene, but-l, 3-ylene, but-l, 4-ylene, but- 2,2-ylene, 2-methylprop-l, 3-ylene, pent-1, 1-ylene, pent-1,2-ylene, pent-l, 3-ylene, pent-l, 4-ylene, pent l, 5-ylene, pent-2,2-ylene, Pent-2,3-ylene, Pent-2,4-ylene, Pent-3,3-ylene, 1-methyl-but-l, 4-ylene, 2-methylbut-l, 4-ylene, etc., preferably with - unless stated otherwise - 2 to 18, in particular 2 to 10 and particularly preferably 2 to 6 carbon atoms.

The lithium salt of the formula (I), 2- {l- [2- (4-chlorophenoxy) propoxyimino] butyl} -3-hydroxy-5- (tetrahydrothiopyran-3-y1) cyclohex-2- enone lithium salt, forms as component (al) at least part of the active ingredient component (a).

The representation of the compound of formula (I) chosen here includes isomeric forms of this compound. Geometric and stereoisomers, such as cis / trans isomers, enantiomers or diastereoisomers, and tautomers, which in the present case are primarily due to the enolate structure, should be mentioned in particular. Accordingly, the compounds of the formula (I) can also be described as a salt of a corresponding cyclohexane-1,3-dione derivative. In addition to the essentially pure isomers, the compound of formula (I) includes its isomer mixtures, e.g. Mixtures of stereoisomers.

In addition to the lithium salt of the formula (I), the active ingredient component (a) can contain one or more further plant active ingredients.

In addition to 2- {l- [2- (4-chlorophenox) propoxyimino] butyl} -3-hydroxy-5- (tetrahydrothiopyran-3-yl) cyclohex-2-enone, further salts or derivatives thereof and others Cyclohexenone oxime ethers and their salts are, for example, agents for combating pests or phytopathogenic fungi or bacteria. In particular, representatives of other herbicidal or growth-regulating groups of active substances are to be mentioned as further plant active compounds. These include, in particular as component (a2), plant active substances which are selected from

- bromobutide, dimepiperate, etobenzanide, propanil,

- Anilofos, Mefenacet,

- 2,4-D and MCPB as metal salts, naproanilides,

Bentazone, especially as sodium salt,

Pyrazolynates / pyrazolates, sulcotrione as metal salt, preferably from the 1st main group,

- Esprocarb, Molinate, Pyributicarb, Thiobencarb / Benthiocarb,

- Quinclorac,

- butachlor, butenachlor, pretilachlor, thenylchlor,

Cycloxydim, sethoxydi, in particular in the form of the sodium and / or lithium salts,

- Pendimethalin,

- (R) -2- [4- (4-Cyano-2-f luorphenoxy) phenoxy] propionic acid n-butyl ester, fenoxaprop-ethyl, - benzofenap, pyrazoxyfen,

- dithiopyr,

- 2,6-bis [(4,6-dimethoxypyrimidin-2-yl) oxy) benzoic acid sodium salt, 2- [(4,6-dimethoxypyrimidin-2-yl) oxy] -6- [l- (methoxyi - mino) ethyl] methyl benzoate,

Azimsulfuron, bensul uron-methyl, cinosulfuron, cyclosulfamuron, ethoxysulfuron, imazosulfuron, pyrazosulfuron-ethyl, advantageously in the form of their metal salts,

- Dimethamethryn, Simetryn / Simetryne, - Benfuresate,

- Cafenstrole,

- cinmethylin, and

- Piperophos.

According to the invention, it is preferred to use the above active ingredients, provided they have acidic OH or NH functions, as agriculturally useful salts, in particular as metal salts with metal cations of the 1st and 2nd main groups.

Of these other crop protection agents, in particular

Salts of Quinclorac with mono- (n = 1) or divalent (n = 2) metal cations M ( ^{n +)} , i.e. carboxylic acid salts of the formula (V)

can advantageously be combined with the lithium salt of the formula (I).

According to one embodiment of the present invention, the active ingredient component (a) consists essentially of the lithium salt of the formula (I). This embodiment relates to oil suspension concentrates based on a herbicidal active ingredient (monopreparation).

According to a further embodiment of the present invention, the active ingredient component (a) consists essentially of a combination of the lithium salt of the formula (I) and a carboxylic acid metal salt of the formula (V). This embodiment relates to oil suspension concentrates based on a herbicidal active ingredient combination (combination preparation).

The respective active ingredient proportions in combination products are largely variable. The active ingredient component typically contains nente (a)

(al) 5-95% by weight, preferably 10 to 70% by weight and in particular 20 to 50% by weight of the lithium salt of the formula (I) and

(a2) 5-95% by weight, preferably 30 to 90% by weight and in particular 50 to 80% by weight of a carboxylic acid metal salt of the formula (V) and

(a3) optionally up to 90% by weight, preferably up to 60

% By weight and in particular up to 30% by weight of a further, preferably herbicidal, plant active ingredient,

wherein the quantitative data each relate to the total weight of the active ingredient component (a) and the sum of the components (al), (a2) and (a3) is 100% by weight in accordance with a particular embodiment.

According to another aspect, the active ingredient component (a) contains relatively larger parts by weight of carboxylic acid metal salts of the formula (V) than the lithium salt of the formula (I). This weight ratio of (I) to (V) is typically in a range from 1: 1.1 to 1: 4, preferably from 1: 1.5 to 1: 3 and in particular from 1: 2 to 1: 2.75.

The purpose of formulation component (F) is to form an oil suspension concentrate based on the lithium salt of the formula (I). Furthermore, parts of the formulation component can have an adjuvant effect, in particular an action-demanding effect.

At least part of the total amount of the lithium salt of the formula (I) present in the oil SC is present as a solid. Another, usually smaller part of the lithium salt of the formula (I) can be dissolved in the formulation component (F). The proportion of dissolved lithium salt of the formula (I), based on the total amount present in the oil SC, is advantageously less than 1% by weight, preferably less than 0.5% by weight and in particular less than 0.3 wt .-%.

The solids content forms a heterogeneous phase in the formulation component (F) (suspension). The solid is advantageously in dispersed form. The formation of stable dispersions is preferred.

Solid active ingredient is usually in particulate form. The average particle size of the active ingredient particles is advantageously usually less than 10 μm and in particular less than 5 μm. Advantageous particle sizes are in a range from 0.1 μm to 10 μm and in particular 0.5 μm to 5 μm. According to a further aspect, advantageous particle size total distributions can be described in that at least 50% of the particles have a particle size of less than 100 μm, preferably less than 50 μm and in particular less than 10 μm. Oil suspension concentrates with total particle size distributions, according to which at least 90% of the active substance particles have a particle size of less than 10 μm and in particular less than 5 μm, are particularly preferred. The above information on particle sizes relates to measurements at room temperature with the Cilas Granulometer 715 from Cilas, Marcoussis, France, whereby solid-saturated samples are measured, which are diluted with the fluid phase of the oil SC according to the invention if necessary.

If the active ingredient component (a) contains one or more further plant active ingredients, these plant active ingredients can in principle be distributed in any form in the formulation component (F). For example, other plant active substances can be present independently of one another at least partially as a solid or in dissolved form. Advantageously, further plant active ingredients contained in the active ingredient component (a) also form a heterogeneous phase. Special configurations of this case result from the above statements on the lithium salt of the formula (I), which apply correspondingly to other plant active substances and in particular to carboxylic acid metal salts of the formula (V).

Thus, in one embodiment, the present invention relates to oil suspension concentrates of the lithium salt of the formula (I) with the active ingredient fractions, solid fractions and / or particle sizes described above. In particular, this includes oil suspension concentrates with a content of lithium salt of the formula (I) of 10 to 30% by weight, a solids content of at least 99% by weight based on the total amount of lithium salt, an average particle size of 1 to 3 μm and a total particle size distribution, according to which typically at least 60% of the particles have a particle size of less than 2 μm.

According to a further embodiment, the present invention relates to oil suspension concentrates of the lithium salt of the formula (I) and at least one carboxylic acid metal salt of the formula (V) with the active ingredient fractions, solid fractions and / or particle sizes described above. The proportion of formulation component (F) is generally 30 to 99% by weight, preferably 50 to 95% by weight and in particular 70 to 95% by weight. Formulation component (F) is usually composed of several components. These components contain auxiliaries, which are primarily used for formulation purposes. In this sense, the components can also be referred to as auxiliary components. However, this term includes further functions and effects of these components, for example active substance-stabilizing and in particular effect-promoting effects.

The formulation component (F) comprises in particular at least one fluid component (b) and at least one surface-active component (c).

The proportion of the fluid component (b), based on the total weight of the oil suspension concentrate, is generally 10 to 90% by weight, preferably 30 to 80% by weight and in particular 40 to 70% by weight.

Component (b) serves primarily as a solvent of soluble constituents or as a diluent of insoluble constituents of the oil suspension concentrate.

At least part of component (b) is formed by one or more oils. According to the invention, the term “oil” denotes a substance that is liquid and practically insoluble in water under the conditions of use of the oil suspension concentrate. Substances in the sense of the invention are insoluble in water when at least 1,000-10,000 parts and preferably at least 10,000 parts of water are required to dissolve one part of the substance.

In principle, for example, mineral oils, synthetic oils and vegetable and animal oils can be used.

These include, above all, aprotic solvents, such as mineral oil fractions of medium to high boiling point, for example kerosene and diesel oil, furthermore coal tar oils, hydrocarbons, paraffin oils, optionally hydrogenated or partially hydrogenated aromatics or alkylates from the benzene or naphthalene series, aliphatic or aromatic carboxylic acid. or dicarboxylic acid esters, in particular the esters of the formulas (Ha) or (Ilb), fats or oils of vegetable or animal origin, such as mono-, di- and triglycerides, in pure form or as a mixture, for example in the form of oily natural substance extracts, for example olive oil, soybean oil , Sunflower oil, castor oil, Sesame oil, corn oil, peanut oil, rapeseed oil, linseed oil, almond oil, ricinus oil, safflower oil, and their raffinates, for example hydrogenated or partially hydrogenated products thereof and / or their esters, in particular methyl and ethyl esters.

The proportion of oil in the total weight of the oil suspension concentrate is generally 10 to 90% by weight, preferably 30 to 80% by weight and in particular 40 to 70% by weight.

According to a particular embodiment, component (b) of oil suspension concentrates according to the invention comprises at least component (b1) specified above.

According to a further special embodiment, the component (b1) specified above is mixed as part of a further formulation (stand-alone product) with the oil suspension concentrates according to the invention at an appropriate point in time, generally shortly before application.

According to the invention, the mono- and dicarboxylic acid esters of the formula (Ha) or (Ilb) belong to the oils. They have long-chain aliphatic residues that can be derived from fatty acids or fatty alcohols. This applies to the meaning of the radicals R ³ and R ⁴ in dicarboxylic acid esters of the formula (IIb) and especially for monocarboxylic acid esters of the formula (Ha) and here in particular to the meaning of the radical R ¹ .

For example, the residues of fatty acids such as tridecanoic acid, lauric acid, elaeostearic acid, undecanoic acid, capric acid, erucic acid, pelargonic acid, caprylic acid, oenanthic acid, caproic acid, isostearic acid, oleic acid, palmitoleic acid, linoleic acid, linolenic acid, arachidonic acid and closahexaenonic acid, clupanodonic acid ,

Accordingly, R ¹ expediently represents a straight-chain or - in particular single - branched, saturated or - up to 6-fold and in particular single - unsaturated, aliphatic radical having 6 to 30 and preferably 8 to 24 carbon atoms. These primarily include the corresponding alkyl and alkenyl residues. A preferred alkyl radical is dodecanyl. A preferred alkenyl radical is octadec-9-enyl, in particular cis-octadec-9-enyl (oleyl).

If the radical R ^{1 stands} for a relatively long-chain radical, the radical R ^{2 is} generally derived from relatively short-chain alcohols. Accordingly, R ² expediently stands for straight-chain or - in particular single or double-branched alkyl having 1 to 8, preferably 1 to 6 and in particular 1 to 4, carbon atoms, or for cycloalkyl, preferably 6 carbon atoms. Preferred alkyl radicals are methyl, ethyl, isopropyl, butyl, 2-ethylhexyl and n- and iso-octyl. Methyl, ethyl and butyl are particularly preferred, and above all methyl. A preferred cycloalkyl radical is cyclohexanyl.

For example, the following monocarboxylic acid esters of the formula (Ha) can be used individually or in combination with one another and with dicarboxylic acid esters of the formula (IIb): oleic acid esters, in particular methyl oleate and ethyl oleate, lauric acid esters, in particular 2-ethylhexyl laurate, octyl laurate and isopropyl laurate, isopropyl myristate, palmitic acid esters, in particular 2-ethylhexyl palmitate and isopropyl palmitate, stearic acid esters, especially stearic acid n-butyl ester and 2-ethylhexanoic acid 2-ethylhexyl ester. Particularly noteworthy are the oleic acid esters, especially methyl oleate.

The radical A ¹ represents a divalent radical which links two carboxyl carbons to one another. For example, A ¹ expediently represents straight-chain or - in particular single - branched alkylene having 2 to 6 and preferably 2 to 4 carbon atoms or cycloalkylene, in particular cyclohexylene. Preferred alkylene radicals are eth-1,2-ylene, prop-1,3-ylene and especially but-1,4-ylene. A preferred cycloalkylene radical is cyclohex-1,2-ylene.

The radicals R ³ and R ⁴ can be different. For practical reasons, especially dicarboxylic acid esters are used in which R ³ and R ^{4 have} the same meaning. In principle, R ³ and R ⁴ can be derived from short and long chain alcohols. Advantageously, R ³ and R ⁴ independently of one another represent a straight-chain or - in particular single - branched, saturated or - in particular 1 or 2 times - unsaturated, aliphatic radical having 1 to 24, preferably 1 to 12, carbon atoms. Above all, this includes the corresponding alkyl and alkenyl residues. Preferred alkyl radicals are methyl and ethyl, but also octyl and nonyl, especially isononyl.

For example, the following dicarboxylic acid esters of the formula (IIb) can be used individually or in combination with one another and with monocarboxylic acid esters of the formula (Ha): adipic acid esters, in particular dimethyl adipate, di-n-butyl adipate, di-n-octyl adipate, di -iso-octyl adipate, also known as bis- (2-ethylhexyl) adipate, di-n-nonyl adipate, di-iso-nonyl adipate and ditridecyla- adipate; Succinic acid esters, in particular di-n-octyl succinate and di-iso-octyl succinate, and di- (iso-nonyl) cyclohexane-1,2-dicarboxy-lat. Dimethyl adipate, bis- (2-ethylhexyl) adipate, di -iso-nonyl adipate.

The proportion of mono- and / or dicarboxylic acid esters of the formula (Ha) or (Ilb), if present, based on the total weight of the oil suspension concentrate, is generally 5 to 70% by weight, preferably 15 to 60% by weight. % and in particular 20 to 50 wt .-%.

In one embodiment, the present invention relates to oil suspension concentrates with a component (b) which is essentially formed from at least one mono- and / or dicarboxylic acid ester of the formula (Ha) or (IIb) (component (bl)).

According to an alternative embodiment, component (b) does not contain a mono- and / or dicarboxylic acid ester of the formula (Ha) or (IIb), but instead at least one further oil as component (b2). This component (b2) can in particular be selected from the oils or aprotic solvents specified above. In particular are here

(b2) at least one Cs to C ₃ o hydrocarbon of the n- or iso-alkane series or a mixture thereof, and aromatic or cycloaliphatic C to Cia hydrocarbon compounds, or a mixture thereof

to call.

Examples of Cs to C ₃ o -hydrocarbons of the n- or iso-alkane series are n- and iso-octane, -decane, -hexadecane, -octadecane, -eicosane, and preferably hydrocarbon mixtures, such as paraffin oil ( which can contain up to about 5% aromatics in technical quality) and a Cχ ₈ -C ₂₄ mixture which is commercially available from Texaco under the name Spraytex oil.

The aromatic or cycloaliphatic C to Cig hydrocarbon compounds include in particular aromatic or cycloaliphatic solvents from the alkyl aromatic series. These compounds can be unhydrogenated, partially hydrogenated or fully hydrogenated. Such solvents of component (b2) include in particular mono-, di- or trialkylbenzenes, mono-, di-, trialkyl-substituted tetralines and / or mono-, di-, tri- or tetraalkyl-substituted naphthalenes (alkyl is preferably Ci -C _ß alkyl). Examples of such solvents are toluene, o-, m-, p-xylene, ethylbenzene, isopropylbenzene, ter-butylbenzene and mixtures, such as the Exxon products sold under the names Shellsol and Solvesso, for example Solvesso 100, 150 and 200.

Component (b2) is preferably selected from at least one, optionally hydrogenated or partially hydrogenated, alkyl aroma from the benzene or naphthalene series, especially from the Exxon products marketed under the trade names Shellsol and Solvesso, for example Solvesso 100, 150 and 200. Accordingly, component (b2) can essentially be formed from said alkyl aromatic compounds. However, it can also contain Cs to C ₃ o -hydrocarbons of the n- or iso-alkane series, which in many cases are included for practical reasons.

The proportion of Ca to C ₃ o -hydrocarbons of the n- or iso-alkane series in the oil suspension concentrates according to the invention should advantageously be less than the proportion of a possible component (bl) or as the proportion of component (b2) , Preferably, the weight ratio of the proportion of o-Cβ- to C ₃ hydrocarbons of the n- or iso-alkane series to Wirksto fanteil less than 3: 1, preferably less than 1.5: 1 and more preferably less than 0.5: 1 ,

In another embodiment, the present invention also relates to oil suspension concentrates having a component (b) which, in addition to at least one mono- and / or dicarboxylic acid ester of the formula (Ha) or (IIb), comprises at least one further oil as component (b2).

In the context of this embodiment, the proportion of mono- and / or dicarboxylic acid esters of the formula (Ha) or (Ilb) is generally 5 to 70% by weight and preferably 15 to 60% by weight and the proportion of further oils (component (b2)) generally 5 to 60% by weight and preferably 10 to 45% by weight.

Advantageously, oil suspension concentrates according to the invention have essentially no or only small proportions of Ci-Cβ-monoalcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, cyclohexanol and 2-ethylhexanol, C 1 -C ₈ -Ketones such as cyclohexanone, and strongly polar solvents such as water.

The proportion of the aforementioned alcohols and ketones, based on the total weight of the oil suspension concentrate, is preferably less than 10% by weight and in particular less than 5% by weight.

The water content of oil suspension concentrates according to the invention, based on the total weight of the formulations, is preferably less than 1% by weight and in particular less than 0.5% by weight. Oil suspension concentrates whose water content is in a range from 0.1 to 0.5% by weight and in particular in a range from 0.05 to 0.25% by weight are very particularly preferred. 0

The proportion of surface-active component (c), based on the total weight of the oil suspension concentrate, is generally 10 to 60% by weight, preferably 15 to 40% by weight and in particular 20 to 30% by weight. 5

Component (c) serves primarily as a dispersant or emulsifier, in particular for dispersing the solids content in the oil suspension concentrate or for emulsifying the oil phase of an oil suspension concentrate given in water. Furthermore, parts 0 of component (c) can serve as wetting agents.

At least part of component (c) is formed by one or more surfactants. The term "surfactant" here denotes surface-active or surface-active agents. 5

In principle, anionic, cationic and amphoteric surfactants can be used, polymer surfactants and surfactants with heteroatoms being included in the hydrophobic group.

The anionic surfactants include, for example, carboxylates, in particular alkali metal, alkaline earth metal and ammonium salts of fatty acids, for example potassium stearate, which are usually also referred to as soaps; glutamates; Sarcosinates, for example sodium lauroyl sarcosinate; taurates; Methylcelluloses; Alkyl phosphates, in particular 5 alkyl and diphosphoric acid alkyl esters; Sulfates, especially alkyl sulfates and alkyl ether sulfates; Sulfonates, especially sulfonates of the formula (HI), further alkyl and alkylarylsulfonates, especially alkali, alkaline earth and ammonium salts of arylsulfonic acids and alkyl-substituted arylsulfonic acids, alkylbenzenesulfonic acids, such as lignin and phenolsulfonic acid, naphthalene acid and dibutylnaphthalenesulfonic acids, or dodecylbenzenesulfonates, alkylnaphthalenesulfonates, alkylmethyl ester sulfonates, condensation products of sulfonated naphthalene and derivatives thereof with formaldehyde, condensation products of naphthalenesulfonic acids, phenolic and / or phenolsulfonic acids with formaldehyde or dialkyl with formaldehyde or with formaldehyde or with formaldehyde or with formaldehyde or with formaldehyde or with formaldehyde or with formaldehyde or with formaldehyde or with formaldehyde or with formaldehyde or with formaldehyde or with formaldehyde or with formaldehyde or with formaldehyde or with formaldehyde, sulfosuccinates; as well as protein hydrolyzates and lignin Liquors. The aforementioned sulfonic acids are advantageously used in the form of their neutral or optionally basic salts.

The cationic surfactants include, for example, quaternized ammonium compounds, in particular alkyltrimethylammonium and dialkyldimethylammonium halides and alkylsulfates, and also pyridine and imidazoline derivatives, in particular alkylpyridinium halides.

The nonionic surfactants include, for example, the compounds of the formula (IV), other alkoxylates and especially ethoxylates, and nonionic surfactants, in particular

Fatty alcohol polyoxyethylene esters, for example lauryl alcohol polyoxyethylene ether acetate,

Alkyl polyoxyethylene and polyoxypropylene ethers, e.g. of iso-tridecyl alcohol and fatty alcohol polyoxyethylene ether, alkylaryl alcohol polyoxyethylene ether, e.g. Octylphenol polyoxyethylene ethers, alkoxylated animal and / or vegetable fats and / or oils, for example corn oil ethoxylates, castor oil ethoxylates, tallow fat ethoxylates, glycerol esters, such as, for example, glycerol monostearate, fatty alcohol alkoxylates and oxo alcohol alkoxylates, in particular of the type

RO- (R ₉ θ) _x (RιoO) yRn with Rg and Rio independently of one another = C ₂ H ₄ , C ₃ H ₆ , C ₄ He and R ₁₁ = H, or Cχ-Ci ₂ alkyl, R = C ₃ -C ₃₀ -AI- alkyl or C ₆ -C ₃ o-alkenyl, x and y independently of one another 0 to 50, where both cannot stand for 0, such as iso-tridecyl alcohol and oleyl alcohol-polyoxyethylene ether, alkylphenol alkoxylates, such as, for example, ethoxylated iso- Octyl, octyl or nonyl phenol, tributylphenol polyoxyethylene ether, - fatty amine alkoxylates, fatty acid amide and fatty acid diethanol amide alkoxylates, in particular their ethoxylates, sugar surfactants, sorbitol esters, such as, for example, sorbitan fatty acid esters (sorbitan monooleate, sorbitan polyoxychloride, sorbitan polyoxychloride, sorbitan polyoxychloride, sorbitan polyoxychloride), , N-alkyl gluconamides,

Alkylmethyl sulfoxides,

- Alkyldimethylphosphine oxides, such as tetradecyldimethylphosphine oxide. The amphoteric surfactants include, for example, sulfobetaines, carboxybetaines and alkyldimethylamine oxides, for example tetradecyldimethylamine oxide.

The polymeric surfactants include, for example, di-, tri- and multiblock polymers of the type (AB) _X , ABA and BAB, for example polyethylene oxide block-polypropylene oxide block-polyethylene oxide, polystyrene block-polyethylene oxide, and AB comb polymers, eg polymethacrylate comb polyethylene oxide.

Further surfactants which are to be mentioned here by way of example are perfluorosurfactants, silicone surfactants, phospholipids, such as, for example, lecithin or chemically modified lecithins, amino acid surfactants, e.g. N-lauroyl glutamate and surface active homo- and copolymers, e.g. Polyvinylpyrrolidone, polyacrylic acids in the form of their salts, polyvinyl alcohol, polypropylene oxide, polyethylene oxide, maleic anhydride-isobutene copolymers and vinylpyrrolidone-vinyl acetate copolymers.

Unless specified, the alkyl chains of the surfactants listed above are linear or branched radicals with usually 8 to 20 carbon atoms.

Component (c) of oil suspension concentrates according to the invention preferably comprises at least one of the surfactant components (cl) and (c2) specified above.

The surfactant component (cl) is formed by at least one anionic surfactant of the formula (III). They are certain sulfonates. These include, in particular, alkanesulfonates and sulfosuccinates, so that R ⁵ expediently represents a straight-chain or - in particular 1 to 2-fold - branched, aliphatic or heteroaliphatic radical having 6 to 30, preferably at least 8 and in particular 12 to 24, carbon atoms. For alkanesulfonates, R ⁵ can be derived in particular from fatty alkyl residues, for example in accordance with a above-mentioned fatty acids. Particular heteroaliphatic radicals are interrupted by one or two ester groups -0C (0) -. In this context, R ¹ in particular stands for succin-2-ylates, mono- and diesters included, and α-linked fatty acid esters.

Sulfosuccinates are preferred anionic surfactants of the formula III. Here R ⁵ stands for a radical -CH (C (0) -0-R ⁷ ) CH ₂ -C (0) -0-R ⁸ , wherein R ⁷ , R ⁸ independently of one another have the meaning given for R ³ and R ⁴ - can accept and especially for alkyl radicals with 1 to 12 and preferably 5 to 8 carbon atoms. A preferred alkyl radical is octyl, in particular iso-octyl.

Due to the negative charge of anionic surfactants, counter cations are necessary, so that M stands for a 1- or 2-valent cation. In principle, any agricultural, inorganic or organic cation is suitable. Cations of metals such as lithium, sodium, calcium, potassium, magnesium, zinc, manganese are preferred, with lithium, sodium and calcium being particularly preferred.

A preferred sulfosuccinate is dioctyl succinate, for example the sodium salt.

The anionic surfactants of the formula III also include alkylarylsulfonates, so that R ⁵ advantageously also represents an alkyl-substituted aryl radical. The aryl radical can be substituted one or more times, in particular two or three times, in which case two substituents can be in the same position, with the same or different alkyl radicals. The alkyl radicals generally have 6 to 30, preferably 10 to 24 and in particular 8 to 12 carbon atoms. Independently of one another, they can be straight-chain or - in particular 1-, 2-, 3- or 4-fold - branched. Decanyl, undecanyl, dodecanyl, tridecanyl and tetradecanyl can be mentioned, for example, of the straight-chain ones, and tetrapropylene, for example, of the branched ones. A preferred aryl radical is phenyl.

A preferred alkylaryl sulfonate is dodecylphenyl sulfonate, for example the sodium, lithium or calcium salt.

If present, the proportion of anionic surfactants of the formula III, based on the total weight of the oil suspension concentrate, is generally 1 to 40% by weight, preferably 7.5 to 30% by weight and in particular 10 to 30% by weight. -%.

The surfactant component (c2) is formed by at least one nonionic surfactant of the formula IV. These are optionally ethoxylated carboxylic acids and esters of monofunctional or polyfunctional alcohols (polyols).

The radical R ⁶ is derived in particular from fatty acid residues, for example those mentioned above, so that R ^{6 is} expediently suitable for a straight-chain or - in particular 1- to 2-fold - branched, saturated or - in particular single, double or triple - unsaturated, optionally mono - or dihydroxylated aliphatic radical with 8 to 30, preferably 12 to 24 and in total special 10 to 24 carbon atoms. These include in particular palmityl, stearyl, arachidyl, hexadecenyl, oleyl, linolyl, linolenyl, ricinoleyl, eggocosanyl and mono- and dihydroxystearyl, of which ricinoleyl and oleyl are preferred.

If the nonionic surfactants of the formula IV are ethoxylated, the sum of all x generally indicates the average ethoxylation number from 3 to 100 and in particular from 5 to 50.

If A ^{2 stands} for hydroxyl, then y = 1 and the average ethoxylation number is advantageously 5 to 50 and preferably 15 to 40. In this context, corresponding castor oil and oleic acid polyethoxylates should be mentioned.

If A ^{2 represents} optionally branched alkyloxy having 1 to 4 and preferably 1 or 2 carbon atoms, then y = 1 and the average ethoxylation number is 3 to 100 and preferably 20 to 50.

If A ^{2 is derived} from a polyol having 3 to 7 and in particular 6 carbon atoms, the value of y = 2 to 7 and preferably 3 to 6. Here, y are hydroxyl atoms of the radical A ² by a radical R ⁶ -CO- ( EO) _x - replaced, where several radicals R ⁶ and several indices x can be the same or different. A plurality of radicals R ⁶ are preferably the same, while the indices x can be different and generally follow a Gaussian distribution. In particular, A ^{2 is derived} from a sugar alcohol, such as sorbitol or glycerin. A preferred meaning of A ² is sorbitol. If ethoxylated, the average ethoxylation number is 5 to 50 and preferably 15 to 40. In this context, the corresponding sorbitol polyethoxy oleates and stearates should be mentioned in particular.

If present, the proportion of nonionic surfactants of the formula IV, based on the total weight of the oil suspension concentrate, is generally 1 to 40% by weight, preferably 2.5 to 25% by weight and in particular 5 to 15% by weight. -%.

In one embodiment, the present invention relates to oil suspension concentrates with a component (c) which is essentially formed by a surfactant component (cl) or a surfactant component (c2).

In a further embodiment, the present invention relates to oil suspension concentrates having a component (c) which is in the is essentially formed by a mixture of the surfactant components (cl) and (c2). In the context of this embodiment, the proportion of surfactant component (cl) is usually 1 to 40% by weight and preferably 7.5 to 30% by weight and the proportion of surfactant component (c2) is generally 1 to 20% by weight. -% and preferably 5 to 10 wt .-%, the respective proportions based on the total weight of the oil suspension concentrate.

In a further embodiment, the present invention relates to oil suspension concentrates with a component (c) which, in addition to the surfactant component (cl) and / or surfactant component (c2), contains further surfactants which can be selected in particular from those described above.

The proportion of further surfactants in the oil suspension concentrates according to the invention should advantageously be less than the proportion of surfactants of the formula (III) and / or (IV). The weight ratio of the proportion of further surfactants to the proportion of active substance is preferably less than 1.5: 1, preferably less than 1: 1 and in particular less than 0.5: 1.

The proportion of the component composed of component (bl), (cl) and / or (c2) is generally greater than 10% by weight, preferably greater than 20% by weight and in particular greater than 25% by weight , This overall proportion is advantageously in a range from 30 to 90% by weight, preferably from 30 to 80% by weight and in particular from 35 to 75% by weight.

Preferred according to the invention are oil suspension concentrates with a formulation component (F) which is based at least in part on a fluid component (bl) in combination with a surfactant component (cl) and / or (c2). Based on the total weight of the oil suspension concentrate, the proportion of the fluid component (bl) together with the surfactant component (cl) and / or (c2) is advantageously 10 to 90% by weight, preferably 15 to 85% by weight and in particular 20 to 70% by weight. Special embodiments of these oil suspension concentrates result from the configurations previously described in relation to components (bl), (cl) and (c2).

Accordingly, according to a particularly preferred embodiment, the present invention relates to oil suspension concentrates based on components (bl), (cl) and (c2). These oil suspension concentrates can in particular also contain a component (b2). If present, the proportion of further auxiliaries as component (d), based on the total weight of the oil suspension concentrate, is generally up to 15% by weight and preferably up to 10% by weight.

Component (d) can serve a variety of purposes. Suitable auxiliaries are usually selected by a person skilled in the art according to the requirements. Stabilizers should be mentioned in particular.

Preferred stabilizers are lithium salts, which can be used as component (dl). These include lithium salts of inorganic or organic acids, in particular lithium hydroxide, lithium carbonate, lithium chloride and lithium carboxylates and sulfonates of organic carboxylic acids and sulfonic acids, in particular the sulfonic acids of the formula (III). Such lithium salts can be dissolved in the oil suspension concentrate or - at least partially - as a solid, for example in particulate and in particular disperse form.

If present, the proportion of component (dl), based on the total amount of active ingredient in lithium salt form, is advantageously 1 to 30 mol% and preferably 3 to 20 mol%.

Anti-settling agents can also be used as stabilizers as component (d2). These serve primarily for the rheological stabilization of oil suspension concentrates according to the invention. Sometimes the thixotropic properties of the formulation can be improved. Above all, the settling of solids and / or agglomeration effects in the oil suspension concentrates should be counteracted. It is desirable to reduce serum formation and / or sedimentation of solids.

Useful anti-settling agents can be found, for example, among the thickeners. These are, in particular, substances which can form a gel-like structure, as a result of which the viscosity of the fluid phase of oil suspension concentrates according to the invention is increased. These include, for example, organic polymers and inorganic substances, in particular finely divided mineral substances such as bentonite, talcite or hectite. Basic mineral systems have proven particularly useful, for example talcites, which may have been converted from the carbonate form to the hydroxide form by calcination.

If present, the proportion of component (d2), based on the total weight of the oil suspension concentrate, is in some cases up to 15% by weight and preferably 1 to 10% by weight.

Stabilizers also include water-absorbing agents that can be used as component (d3). Alkaline boron salts, in particular anhydrous, calcined or dewatered boron salt of the borax type, are to be mentioned in this connection.

If present, the proportion of component (d3), based on the total weight of the oil suspension concentrate, is advantageously up to 15% by weight and preferably 2 to 10% by weight.

In addition to the active ingredient component (a) and the formulation component (F), the oil suspension concentrates according to the invention can contain further additives. Of interest, for example, is the miscibility with mineral salt solutions, which are used to remedy nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates as well as anti-drift reagents can also be added. Antisheck agents are also suitable, in particular those of the silicone type, for example the Silicon SL marketed by Wacker, which can be added in an amount of 0.1 to 10 g and preferably 1 to 2 g per liter.

Oil suspension concentrates according to the invention can be prepared in a manner known per se. For this, at least parts of the components are put together. It should be noted here that products, in particular commercial products, can be used, the components of which can contribute to different components. For example, a particular surfactant can be dissolved in an aprotic solvent so that this product contributes to both component (b) and component (c). Small amounts of undesirable substances, such as water or lower alcohols or ketones, can also be introduced with commercially available products. The products to be processed into oil SCs according to the invention are therefore advantageously selected from the aspect of the lowest possible content of water and / or lower alcohols or ketones. As a mixture, in particular in the form of a suspension, the combined products are generally to be ground intensively.

Glass grinding media or other mineral or metallic grinding media, generally in a size of 0.1-30 mm and in particular of 0.6-2 mm, can be used as grinding media. Man crush The mixture is usually kept until the desired particle size is reached.

In general, grinding in a circular mode, i.e. 5 pumping around the oil SC in a circle, or by means of passage mode, i.e. complete and repeated pumping or driving through an oil SC approach.

The grinding can be done with conventional ball, bead or agitator mills, e.g. in a Dynomuhle (from Bachofen), with batch sizes of, for example, 0.5 to 1 liter in the so-called passage mode. After several - in particular 4 to 6 - passages (pumping the slurry through the mill with the help of a peristaltic pump), 5 average particle sizes of 0.5 to 10 μm are reached after microscopic evaluation.

Subsequently, additional aids can be incorporated, e.g. by homogenizing with suitable devices such as KPG or magnetic stirrers.

There are several possible production variants, for example direct grinding or blending from an oil suspension concentrate preconcentrate. 5 The major part of the component is used for direct grinding

(b) submitted together with component (c) and the active ingredient component (a) added as a solid. The formulation batch is then filled with the remaining amount of component (b). The mixture is then ground as described above. Any component (d) to be added can be added at any time. It is preferred to also grind the stabilizing agents, especially inorganic stabilizers. The grinding can be carried out together with the active ingredient. However, they can also be ground separately, for example as so-called master batches, in which case a higher concentration is usually processed, which is then added to the oil suspension concentrate.

₀ For the mixing from the oil suspension concentrate preconcentrates, the active ingredient component (a) is first milled with part of the component (b) to form a preconcentrate in the manner described above. Subsequently, the preconcentrate is initially charged and admixed with component (c) and adjusted by adding further com- _g component (b) to the desired active substance content. Here too, component (d), if present, can be added at any time. It is also preferred to stabilize Adding agents during grinding.

The lithium salt of the formula (I) can be used as a solid in the preparation of the oil suspension concentrates.

Process suitable in principle for the preparation of 2- {l- [2- (4-chlorophenox) propoxyimino] butyl} -3-hydroxy-5- (tetra-hydrothiopyran-3-yl) -cyclohex-2-enone lithium salt Formula (I) are, for example explained in WO 97/20807. This includes the reaction of 2- {l- [2- (4-chlorophenoxy) propoxyimino] butyl} -3-hydroxy- (5-tetrahydrothiopyran-3-yl) -cyclohex-2-enone of the formula (ia )

with a basic lithium salt and obtaining the compound of formula (I). Suitable basic lithium salts are, for example, appropriate hydrides, hydroxides, alcoholates or carbonates. Furthermore, the lithium salt of the formula (I) can be prepared from the corresponding cyclohexenone oxime ether sodium salt by sodium / lithium exchange.

The compound of the formula (Ia) is preferably reacted with lithium hydroxide in a solvent mixture comprising methanol and at least one aromatic hydrocarbon and at least part of the solvent is removed before the compound of the formula (I) is obtained. Useful aromatic hydrocarbons particular solvent of ^'the benzene series, such as alkyl-substituted benzenes, such as toluene and xylene belong. Toluene is particularly suitable. A solution of compound (Ia) in toluene is preferably used. The concentration of the compound of the formula (Ia) is preferably 5 to 40% by weight, preferably 10 to 30% by weight and in particular approximately 20% by weight, based on the total weight of the solution to be used. Lithium hydroxide (LiOH) can be used, for example, in anhydrous form or as a hydrate, in particular a monohydrate. A solution of LiOH is preferably used, which is based on methanol, but may also contain other solvents in addition to this. Preferred are methanolic LiOH solutions which, in addition to possible white tere solvents contain at least 70 wt .-%, preferably at least 80 wt .-% and in particular at least 85 wt .-% methanol, based on the total amount of solvent of the LiOH solution to be used. A methanolic LiOH solution advantageously contains 1 to 7% by weight, preferably 2 to 6% by weight and in particular approximately 5% by weight of LiOH. The amounts given relate to the total weight of the solution used before addition. To ensure complete implementation, the lithium hydroxide solution is usually used in a molar excess. A molar excess of 0.5 to 10%, based on the cyclohexenone oxime ether (Ia) used as the starting product, is preferably used. However, it can also make sense to react lithium hydroxide in a molar ratio of 1: 1 with the cyclohexenone oxime ether (Ia). In this case, for example, the addition of LiOH, in particular as a lithium hydroxide solution, can be monitored with a suitable pH electrode and metered in until the equivalence point is reached. The dosing times for the respective reactants are usually in the range from 10 minutes to 360 minutes, preferably 10 minutes to 120 minutes, in particular around 30 minutes. The reaction is usually carried out at temperatures of −20 ° C. and 60 ° C., preferably 0-40 ° C., particularly preferably 20-30 ° C. Before the cyclohexenone oxime ether salt (I) is obtained, at least part of the solvent mixture, in particular methanol, is removed from the solvent mixture. This is usually done together with other components of the solvent mixture, in particular as a methanol / toluene / water mixture. The removal is preferably carried out by distillation, usually at temperatures between 20 and 70 ° C, preferably at 30-60 ° C and particularly preferably at 40-50 ° C. The distillation can be carried out under normal pressure or preferably under reduced pressure. A suspension is formed. Accordingly, it may be expedient to remove so much solvent that the compound of the formula (I) precipitates essentially completely. According to a special aspect, methanol is essentially completely removed from the reaction mixture. The cyclohexenone oxime ether lithium salt (I) is usually obtained by subjecting the resulting suspension to a solid / liquid separation. Filtration, in particular pressure filtration, belt filtration, vacuum filtration, centrifugation, and the like, are preferred. A cleaning of the separated solid, in particular in the form of a filter cake, is generally advisable. This can be done with a suitable solvent, especially toluene. As a rule, it is also expedient to dry the separated solid, in particular the filter cake. A special form of the product obtainable by this process has a (I) content of at least 96% by weight, preferably of at least 97% by weight and in particular of at least 98 % By weight, based on the total weight of the product obtained.

This process not only allows the process product to be obtained comparatively more efficiently, but the cyclohexenone oxime ether Li salts (I) which can be prepared by this process surprisingly form relatively more stable oil SC formulations. This is particularly important for use as a rice herbicide and, according to another aspect, for use in the tropical area. It is advantageous to be able to ensure a comparatively high long-term storage stability at an elevated temperature in the range of 30-40 ° C.

The lithium salt of the formula (I) can also be generated quasi in situ during the preparation of the oil suspension concentrate. This is achieved, for example, by grinding the acid of the formula (Ia) together with appropriate amounts of lithium hydroxide instead of the lithium salt of the formula (I). Released water can be bound or removed. For this purpose, for example, the water-binding agents described above as component (d3) can be used, or it can be distilled off azeotropically, for example in the presence of toluene.

The present invention also relates to the use of oil suspension concentrates according to the invention as crop protection agents in agriculture. This use includes a method for the treatment of plants in which an effective amount of at least one oil suspension concentrate according to the invention is applied.

Depending on the respective application method, the oil suspension concentrates according to the invention can be used in a large number of crops and ornamental plants for eliminating unwanted plants. The following crops are considered, for example:

Allium cepa, pineapple comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spp. altissima, Beta vulagris spp. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Ca ellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea libericaus), Cucumodison dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Ficus elastica, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, Iumomouglulus, Humulus lupulus, Humulus lupulus Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot esculenta, Medicago sativa, Musa spp., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spp. Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (s. Vulgäre), Theobroma cacao, Trifolium pratense, Triticitic fumum, Triticitic fumum Vitis vinifera, Zea mays.

Oil suspension concentrates according to the invention are used in particular as grass herbicides and above all for rice crops.

For this purpose, the oil suspension concentrates according to the invention are usually converted into a form usable for use by dilution in the customary manner. Dilution with water or aprotic solvents is preferred, for example using the tank mix method for aircraft application (ULV application). Use in the form of a spray mixture is preferred. It is usually applied pre- or post-emergence.

The presence of a practically water-free oil-based formulation also enables application in the ULV process (ultra low volume). B. by aircraft application.

For a conventional tank ix spray liquor, 0.25 to 5, preferably 0.5 to 2.0 1, of the oil suspension concentrate according to the invention are diluted with water to 5 to 2,000 1 per ha. For a ULV tank mix spray liquor, 0.25 to 10 1, preferably 0.5 to 5 1, of the oil suspension concentrate according to the invention is applied to 5 to 50 1 per ha with an oil phase, preferably an oil of component (b), for example a Spraytex Oil, or diluted with water or a mixture of water and oil in a volume ratio of about 2: 1 to 4: 1. The tank mix spray liquor may be used

0.1% by weight to 5% by weight (based on the spray mixture) of further anionic, cationic or nonionic surfactants, auxiliaries, polymers and / or the abovementioned other herbicidal active ingredients. Exemplary substances for such surfactants and other auxiliaries have already been described above. In particular, starch and starch derivatives, for example a starch containing carboxyl and sulfonic acid groups (Nu-Film from Union Carbide Corp.) and spreading agents and extenders, such as Vapor Guard from Miller Chemical & Fertilizer Corp., should be mentioned. The invention is illustrated by the following examples:

Preparation Examples

Reference Example 1: Lithium Salt of Formula (I)

702.78 g (0.400 ol) of a 26, 5% toluene solution of the cyclohexenone oxime ether (Ia) are introduced at 25 ^C C with stirring and diluted with 229.47 g of toluene, thereby adjusting a concentration of cyclohexenone oxime ether (Ia) of 20% becomes. 200.98 g (0.420 mol) of a 5% LiOH solution (calcined LiOH (98+); chemetallic) in MeOH are then added within 30 min. The mixture is stirred at 25 ° C for 1 h. Then 370.59 g of a MeOH / toluene / water mixture are distilled off at 50 ° C. in vacuo. The temperature is kept at 50 ° C and the pressure is reduced from 450 mbar to 100 mbar. The distillation time is 210 min. After the distillation is complete, 13 g of methanol are added, the mixture is stirred at room temperature for 15 minutes and the suspension is drained from the stirred tank and placed on a pressure filter filter. When the filtration has ended, the stirred tank is rinsed out with 174.00 g (200 ml) of fresh toluene and the filter cake is washed with this rinsing toluene. The filter cake is then washed twice with 87.0 g (100 ml) of fresh toluene. The filter cake is then dried in a vacuum drying cabinet at 50 ° C. for 24 hours. 181.01 g of filter cake with a content of 98.2% are obtained. Taking this content into account, the yield is 94.1%.

Reference example 2: Oil suspension concentrate by direct grinding (D):

About 90% by weight of component (b) are initially charged with the total amount of component (c). The active ingredient component (a) is added as a solid powder (reference example 1). The formulation batch is then made up to 1 liter with the remaining amount of component (b). The batch is then ground using glass beads (0.9-1.2 mm) as grinding aid at approx. 0 ° C. in a Dynomuhle from Bachofen using a passage procedure until a total particle size distribution is reached, after which approx. 60% of the Particles have a particle size of less than 2 μm. Typically 5 passages are required. Reference Example 3: Oil Suspension Concentrate by Blending Active Ingredient Concentrate (A)

The active ingredient component (a) is ground with about 30% by weight of component (b), as described above, to form a preconcentrate. The preconcentrate is then introduced, mixed with component (c) and adjusted to the desired active ingredient content with residual portions of component (b).

Examples 1 to 23: Oil suspension concentrates

Using the production variant (D) or (A), oil suspension concentrates are produced in accordance with the information in Table 2 below (Examples 1 to 23).

Table 2: Active ingredients and auxiliaries of certain oil suspension concentrates, given as ["name" / "g / kg oil suspension concentrate"], unless stated otherwise

Example 24: EC formulation

436.4 g of a 34.4% toluene solution of (Ia) were stirred with evaporation of toluene for 5 hours at 40 ° C. and 20-30 mbar on a rotary evaporator and then aftertreated for 3 hours at 1 mbar and room temperature. The oily residue was then taken up with twice the amount of Solvesso 150. Then the auxiliaries corresponding to components (b) and (c) of Example 23 given below were stirred in and made up to 1 L with Solvesso 150. 24 Ia / 150 Me-Oleat / 200 Aerosol OT-A / 250 D Solvesso 150 / ad 11 Emulpon EL 20/50

The auxiliaries used in the above examples are explained in Table 2 below.

Table 2:

Physical properties: stability and emulsification behavior

The evaluation of the stability of oil suspension concentrates (Examples 1 to 22 is examined in a rapid storage test.

For this purpose, the samples are in closed glass containers 14

Stored at 54 ° C for days. Then the active ingredient concentration tion determined. This value in relation to the original active substance content is a measure of the stability of the oil suspension concentrate.

The emulation behavior is assessed after visual assessment based on the CIPAC MT 180 method in a 100 ml syringe. A 2% by weight mixture of the oil suspension concentrate in water is prepared. The following evaluation scale is applied: ++ _: no cream or sediment;

+: little cream or sediment, <0.1 ml; +/-> 0.1 <0.5 ml cream or sediment; (-)> 0.5 ml cream or sediment, inhomogeneous sample.

The following table 3 summarizes the stability data and the assessment of the emulsification behavior of certain oil suspension concentrates.

Table 3:

nb: Not determined due to insufficient active ingredient stability

In particular, the oil suspension concentrates according to the invention according to Examples 1 to 9 and 20 to 23 are distinguished by excellent storage stability. The emulsifying behavior is satisfactory.

The formulations from Examples 23 and 24 were stored in 50 ml ampoules at 50 ° C. The relative residual proportions of the active ingredient (I) b2w. (Ia), determined analytically in each case as free acid, are shown in Table 4 below.

Table 4:

Accordingly, Ol-SC formulations according to the invention based on the active ingredient salt (I) have a much better storage stability than EC formulations based on the free active ingredient acid (Ia).

Biological properties

Field trials with various herbicide combinations in rice were carried out as a randomized block system with 3 or 4 repetitions. The plot size of the experiments varied between 2 - 6 m ² . All treatments of the products were applied with a backpack syringe. The backpack sprayer was equipped with a spray rake with 4 or 6 flat jet nozzles. The products were applied with a water volume of 300 1 / ha. The rice culture was fertilized according to the standard recommendation. Due to the low weed population, 5 - 10 kg / ha of weed was additionally sown by hand per broad seed. Experiments with strong broad-leaf and Cyperus weeds were applied 7 days after the application of the graminicides with bentazone or 2,4-D in order to avoid interactions. The developmental stages of the rice and weeds were determined according to the BBCH scale (Strauss R. 1994: Compendium of Growth Stage Identification Keys for Mono- and Dicotyledonus Plants. Extended BBCH-Scale, ISBN 3-9520749-0-X) , The selectivity and the herbicidal activity were determined in accordance with the EPPO guideline (OEPP / EPPO 1998: Guideline for the Efficacy Evaluation of Herbicides - Weeds in Paddy Rice - EPPO Standard 1/62 (2). In: Guidelines for the Efficacy Evaluation of Plant Per- tection Products, Vol. 4, Herbicides and Plant Growth Regulators).

Table 5 below summarizes the results of the field tests carried out.

Table 5:

ECHCG: Echinocloa crus-galli

LEFCH: Leptochloa Chinese

A amount: application rate based on the amount of active ingredient

These experiments show that the auxiliary component (b1) according to the invention, here in the form of methyl oleate, causes relatively little plant damage with a generally good effect on grasses.

Claims

claims

1. Oil suspension concentrate comprising

(al) 2- {l- [2- (4-chlorophenoxy) propoxyimino] butyl} -3-hydroxy-5- (tetrahydrothiopyran-3-yl) cyclohex-2-enone lithium salt of the formula (I)

and

at least one component selected under

(bl) at least one mono- and / or dicarboxylic acid ester of the formula (Ha) or (Ilb),

Ri-CO-OR ² (Ha)

R ³ - _O -C0-A -.- _C O-0-R ⁴ (Ilb ₎

where R ^{1 is} a straight-chain or branched, saturated or unsaturated aliphatic radical having 6 to 30 carbon atoms, R ^{2 is} straight-chain or branched alkyl or cycloalkyl, A ^{1 is} straight-chain or branched alkylene or cycloalkylene and R ³ , R ⁴ independently of one another straight-chain or branched, saturated or unsaturated aliphatic radical having 1 to 24 carbon atoms;

(cl) at least one anionic surfactant of the formula III,

R ⁵ -S0 ₃ - 1 / n M ^{(n +)} (HI) where M is a mono- or divalent cation (n = 1 or 2) and R ^{5 is} a straight-chain or branched, aliphatic or heteroaliphatic radical having 6 to 30 carbon atoms or a (Ce-C ₃ o-alkyl) aryl radical, and

5 (c2) at least one nonionic surfactant of the formula IV,

[R ⁶ -CO- (EO) _x -] _y A ² (IV)

wherein R ⁶ is a linear or branched, saturated or unsaturated, optionally mono- or dihydroxylated aliphatic radical having from ₀ 8 to 30

Carbon atoms, the sum of all x is zero to 100, y is 1 to 7, A ^{2 is} hydroxy or alkyloxy if y is 1, or A ² is derived from a polyol if y is 2 to 7.

2. An oil suspension concentrate according to claim 1, comprising

^ (al) the lithium salt of formula (I) and

(a2) at least one further herbicidal plant active ingredient.

3. Oil suspension concentrate according to claim 2, which as a further herbicidal crop protection agent, a carboxylic acid metal salt of the formula (V)

contains. 5

4. Oil suspension concentrate according to one of the preceding claims, wherein the component (bl) is selected from Ci-Cs-alkyl esters of oleic acid, di- (-CC ₂ -alkyl) esters of adipic acid and mixtures thereof.

5. Oil suspension concentrate according to one of the preceding claims, comprising a component (b2) which is selected from at least one, optionally hydrogenated or partially hydrogenated, alkyl aromatics from the benzene or naphthalene series.

6. Oil suspension concentrate according to one of the preceding claims, wherein the component (cl) is selected from

Di (-C 1 -C ₂ alkyl) sulfosuccinates, (C ₆ -C ₃ o-alkyl) benzenesulfonates and mixtures thereof.

7. Oil suspension concentrate according to one of the preceding claims, wherein the component (c2) is selected from castor oil polyethoxylates, sorbitol polyethoxypleates and mixtures thereof.

8. Oil suspension concentrate according to one of the preceding claims, comprising component (s) (cl) and / or (c2).

9. Oil suspension concentrate according to claim 8, comprising component (bl) and component (s) (cl) and / or (c2).

10. Oil suspension concentrate according to one of the preceding claims, comprising

(d) at least one further component which is selected from

(dl) lithium salts,

(d2) anti-settling agents and

(d3) water-binding agents.

11. Use of an oil suspension concentrate according to one of claims 1 to 10 as a crop protection agent in agriculture.

12. Use according to claim 11 as a rice herbicide.